Rich Structure Chemistry in the Aluminophosphate Family - American

Acc. Chem. Res. 2003, 36, 481-490

Rich Structure Chemistry in the Aluminophosphate Family JIHONG YU AND RUREN XU* State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130023, People’s Republic of China Received September 20, 2002 ABSTRACT This Account describes a family of aluminophosphates ranging from neutral open-frameworks to anionic frameworks with fascinating structural architectures. In contrast to aluminosilicate zeolites, these aluminophosphates exhibit wealthy structural features, including extra-large micropores, mixed bonding, different structural dimensionalities, rich compositional diversities, and various stacking sequences of their 2-D sheets. The low-dimensional networks, acting as building units, can be assembled to 3-D open-frameworks via transition metal cations through a buildingup process. New stoichiometries and hypothetical structural topologies can be predicted and enumerated. Computational and combinatorial approaches will greatly help to access the range of the diverse structures.

Introduction Inorganic open-framework materials with regular pore architectures, typically known as zeolites, constitute an important area of materials science because of their widespread applications in catalysis, separation, and host-guest assemblies. Traditionally, zeolites refer to a class of crystalline aluminosilicates constructed from TO4 tetrahedra (T ) Si and Al) to form structures of composition Ax/n[Si1-xAlxO2]‚mH2O, where A is a metal cation of valence n and 0 e x e 0.5.1 In 1982, Wilson and co-workers developed a new class of zeolite-like molecular sieves AlPO4-n (n denotes a structure type).2 Their structures are typically built up from strict alternation of AlO4 and PO4 tetrahedra through corner sharing to form a neutral openframework. Part of the Al sites can be replaced by catalytically active transition metal ions. One of the important promising areas of application shown very recently is in catalysis where aerial oxidations are possible using linear and cyclic hydrocarbons.3 They are also available in the growing field of solvent-free industrial reactions in the important area of clean technology.4,5 The discovery of AlPO4-n has been promoting enormous growth in the chemical diversity of open-framework

Jihong Yu, born in 1967 in Liaoning, received her B.S., M.S., and Ph.D. from Jilin University and worked at the Hong Kong Science and Technology University and Tohoku University. Since 1999 she has been Professor in the Chemistry Department, Jilin University. Her research interest is the design and synthesis of inorganic open-framework materials. Ruren Xu, born in 1932 in Zhejiang, received his B.S. from National Shanghai Jiaotong University and worked at Fu Dan University and Hamburg University. Since 1979, he has been Professor in the Chemistry Department, Jilin University. His research interest is molecular engineering of inorganic open-framework materials. He is an Academician of the Chinese Academy of Sciences and a Councilor of International Zeolite Association. 10.1021/ar0201557 CCC: $25.00 Published on Web 03/27/2003

 2003 American Chemical Society

metal phosphates, including aluminophosphates, gallophosphates, and zincophosphates, and transition metal phosphates,6-8 among which aluminophosphates (hereafter denoted AlPO’s) display rich variety of structures, including neutral zeolite-like open-frameworks, and a range of anionic open-frameworks with 3-dimensional (3D) framework, 2-D layer, 1-D chain, and 0-D cluster structures. The structures of anionic AlPO’s are made up of alternation of Al-centered polyhedra (AlO4, AlO5, AlO6) and P-centered tetrahedra P(Ob)n(Ot)4-n (b, bridging; t, terminal; n ) 1, 2, 3, 4) to form diverse stoichiometries, including AlPO4(OH)-, AlP4O16,9- AlP2O83-, Al2P3O123-, Al3P4O163-, Al3P5O206-, Al4P5O203-, Al5P6O243-, Al11P12O483-, Al12P13O523-, Al13P18O7215-, and so forth (Table 1).9-14 Their frameworks exhibit fascinating structural architectures; for example, JDF-20 has the largest channel ring size of 20 among open-framework AlPO’s,15 and AlPO-CJB1 is the first aluminophosphate molecular sieve with Bro¨nsted acidity.13 The structure chemistry of open-framework AlPO’s is strikingly different from that of aluminosilicate zeolites for several reasons. First, the Al atom in AlPOs can be mixedbonded adopting four, five, and/or six coordination with oxygen,16 in contrast to the strict occurrence of fourcoordinated Al in aluminosilicate zeolites. The tetrahedral P atom can share its one, two, three, or four oxygen atoms with adjacent Al atoms. The rich stoichiometries of AlPO’s are attributed to the diverse coordinations of Al and P atoms. However, in zeolites the Si/Al ratio is dependent on the states and distribution of polysilicate anions in the framework. Second, the strict alternation of Al polyhedra and P tetrahedra in AlPO’s defines an even number ring of T atoms such as 8, 10, 12, 14, 18, and 20, which prevents the occurrence, for example, of five-ring units commonly encountered in aluminosilicate zeolites. Third, the diverse structures of AlPO’s are greatly facilitated by utilization of various organic amine templates which interact with the host frameworks through H-bonds. As a consequence, some frameworks of AlPO’s are not thermally stable compared to aluminosilicate zeolites whose structures are facilitated by some inorganic cations or quanternary ammonium cations. In this Account, we will describe the structure chemistry of aluminophosphates with neutral open-framework, extra-large micropore, anionic 3-D, and low-dimensional framework structures. Approaches toward the design and synthesis of these materials are introduced.

Neutral Open-Framework Aluminophosphates The initiation of aluminophosphate molecular sieves AlPO4-n is based on the crystal chemistry principle that AlPO4 is isoelectronic with SiO2.2 In AlPO4-n, both Al and P atoms are tetrahedrally coordinated by oxygen atoms and alternate on the framework. There are no Al-O-Al and P-O-P connections allowed due to the Lowenstein’s rule. Their Al/P ratio is exclusively of unity, and their framework is neutral in contrast to negatively charged VOL. 36, NO. 7, 2003 / ACCOUNTS OF CHEMICAL RESEARCH

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Rich Structure Chemistry in Aluminophosphate Family Yu and Xu

Table 1. Anionic Aluminophosphates with Various Dimensionalities, Stoichiometries and Coordinations (Al/P e 1)a dimensionality stoichiometry 3-D

2-D

1-D 0-D a

Al12P13O523Al11P12O483Al5P6O243Al4P5O203Al3P4O123Al13P18O7215Al4P5O203Al3P4O163Al3P4O163Al2P3O123Al2P3O123AlP2O83AlP2O83AlPO4(OH)Al3P5O206AlP2O83AlP2O83AlP4O169-

Al and P coordinations AlO4b, AlO5b, PO4b AlO4b, AlO6b, PO4b AlO4b, PO4b, PO3bOt AlO4b, AlO5b, PO4b, PO2bO2t AlO4b, PO3bOt AlO6b, AlO4b, PO3bOt AlO4b, AlO5b, PO4b, PO3bOt, PO2bO2t AlO4b, AlO5b, PO4b, PO3bOt, PO2bO2t AlO4b, PO3bOt AlO4b, AlO5b, PO4b, PO3bOt, PO2bO2t AlO4b, PO3bOt, PO2bO2t AlO4b(H2O)2, PO2bO2t AlO4b, PO2bO2t AlO3b(OH), PO3bOt AlO4b, PO3bOt, PO2bO2t, PObO3t AlO4b, PO2bO2t AlO4b, PO3bOt, PObO3t AlO4b, PObO3t

b, bridging oxygen; t, terminal oxygen.

aluminosilicate zeolites.6 So far, more than 20 types of neutral open-framework aluminophosphate molecular sieves have been reported in the latest issue of the Atlas of Zeolite Structure Types.17 Some aluminophosphates have structures analogous to known aluminosilicate zeolites, whereas others have not been found to have zeolite counterparts yet. The majority of AlPO4-n’s possess a (4,2)-connected framework, that is, the primary building units are fourconnected tetrahedral nodes (Al or P), and the bridges between those nodes are two-connected atoms (O). However, there is a number of AlPO4-n that have a framework deviated from the ideal (4,2)-connection. These include the mixed-bonded framework containing five- or six-coordinated Al atoms with one or two extraframework oxygen species (OH or H2O), as well as four-coordinated Al atoms.

Extra-Large Micropore Aluminophosphates VPI-5 is the first molecular sieve that contains rings greater than 12 T-atoms.18 It sets up the state for the development of numerous other extra-large micropore materials. Figure 1a illustrates the topology of VPI-5. It contains rings of 18 T-atoms. Its structure is made up of AlO4, AlO4(H2O)2, and PO4 units. Two water molecules bond to the Al atom at the center of the fused four-rings of trans conformation.19 The structure of VPI-5 can transform to AlPO4-8 with 14-rings of pore openings upon heating (Figure 1b).20 During the phase transformation, the six coordination of Al is still preserved. An interesting question is whether an aluminosilicate or a pure silica zeolite analogue of VPI-5 exists. Assuming a (4,2)-connected pure SiO2 analogue of VPI-5 followed by DLS refinement,21energy calculation results indicate that the hypothetical analogue has an extremely high Urey-Bradley energy of 1.760 kcal/mol per SiO2 unit compared to the values of 0.027, 0.120, 0.123, and 0.23 for silica zeolite CHA, LEV, ERI, and SSZ-24 analogues to AlPO4-34, -35, -17, and -5, respectively. The unfavorable 482 ACCOUNTS OF CHEMICAL RESEARCH / VOL. 36, NO. 7, 2003

FIGURE 1. (a) Framework topology of VPI-5 (bridging oxygens are omitted). (b) Phase transformation from VPI-5 to AlPO4-8 (waters are not shown). Si(Al)-O-Si linkage in the fused edge-sharing four-rings limits the possibilities of aluminosilicate or pure silica zeolite analogue of the VPI-5 structure. The structure of VPI-5 suggests a possible way to facilitate the formation of extra-large micropore by introducing mixed-bonded Al atoms in the framework. The alternative approach to the extra-large micropore is to make an interrupt framework. This situation is encountered in the extra-large micropore aluminophosphate JDF20 (Jilin-Davy Farady, 20-membered ring).15 JDF-20, [Al5P6O24H]‚2Et3NH‚H2O, contains 20-membered ring (MR) channels with elliptical apertures along c intersected by 10- and 8-MR rings (Figure 2). Its structure is made up of alternation of AlO4 and PO4 tetrahedra in which all the Al vertexes are shared, but two-thirds of the PO4 tetrahedra have a terminal P-O bond. Its secondary building unit (SBU) is composed of five Al atoms and six P atoms. Its structure is featured by two types of 1-D chains along c, i.e., corner-sharing 4-MR chains and zigzag edge-sharing 4-MR chains. The entrance to the main channel has oxygen atoms protruding into it. Such structural feature is also found in the extra-large micropore gallophosphate cloverite.22

Anionic 3-D Open-Framework Aluminophosphates It is noticed that the Al/P ratio of JDF-20 deviates from unity encountered in neutral open-framework AlPO4-n.


FIGURE 3. Structure of AlPO-HDA viewed along b (its SBU and characteristic columns of D6Rs are shown).

FIGURE 2. Framework of JDF-20 (its SBU and the linear cornersharing 4-MR chain (1) and zigzag edge-sharing 4-MR chain (2) are shown). The existence of terminal P-O bonds results in not only an interrupted structure but also an anionic framework with Al/P ratio less than 1. As with JDF-20, a number of aluminophosphates has been found to possess anionic frameworks with Al/P ratios less than unity (Table 1). AlPO-HDA, [Al4P5O20H][C6H18N2], has an Al/P ratio of 4/5.23 It is made up of alternation of Al units (AlO4 and AlO5) and P units (PO4, PO2(dO)(OH)) to form an interrupted open-framework structure with interconnected 12and 8-MR channels along b and c, respectively (Figure 3). Its SBU is a branched three edge-sharing 4-MRs. The framework is featured by of a series of columns of D6Rs along b. [Al2P3O12][C4H16N3] (AlPO-DETA) has an Al/P ratio of 2/3.24 It is built up from alternation of tetrahedral AlO4 units and PO4 (PO3(dO) and PO2(dO)2) units via oxygens. It consists of parallel 12- and 8-MR channels along [001]

FIGURE 4. Framework of AlPO-DETA viewed along [001] (a) and [010] (b) (its SBU and SBU chain are shown). and 8-MR channels along [010] (Figure 4). Its SBU is composed of a branched 4-MR. Such SBU’s are connected together to form infinite chains along a, which are further connected through vertex oxygens to form the 3D openframework. [AlP2O6(OH)2][H3O] (AlPO-CJ4) has an Al/P ratio of 1/2.25 It is constructed from alternation of AlO6 octahedra and PO3(OH) tetrahedra via vertex oxygens to form a 3-D open framework with interconnected 8-MR channels along a, b, and c, respectively (Figure 5). As seen in the SBU, the Al units are solely made up of AlO6 octahedra, with all six oxygen vertexes being shared by adjacent P atoms. The structure features a series of chiral propellerlike motifs comprised of Al-centered octahedron with three cyclic 4-MRs. 3-D anionic open-framework [Al9(PO4)12][C24H91N16]‚ 17H2O with an Al/P ratio of 3/4 has also been reported.26 VOL. 36, NO. 7, 2003 / ACCOUNTS OF CHEMICAL RESEARCH 483


open-framework aluminophosphates show vast structural and compositional diversities compared to aluminosilicate zeolites.

Low-Dimensional Anionic Framework Aluminophosphates

FIGURE 5. Framework of AlPO-CJ4 viewed along c (its SBU and chiral propeller-like motif are shown). Its structure is made up of alternation of AlO4 and PO3(dO) tetrahedra. Unlike neutral open-framework AlPO4n, the frameworks described above are all negatively charged, whose charge neutrality is achieved by protonated organic amine or water molecules occluded in the channel. These anionic AlPO’s may have a potential to possess Bro¨nsted acidity and ion-exchange capacity like aluminosilicate zeolites once the template molecules are removed to leave protons to balance the negative charges. However, for most of anionic AlPO’s, the removal of the occluded templated molecules by calcination is not so successful. Efforts have been made to try to remove the templates by other ways. [Al12P13O52]3-[(CH2)6N4H3]3+ (AlPO-CJB1) is the first aluminophosphate molecular sieve possessing Bro¨nsted acidity upon removal of the templates by calcination.13 Its framework is constructed by strict alternation of Alcentered polyhedra (AlO4 and AlO5) and P-centered PO4 tetrahedra by sharing all oxygen atoms at vertexes to form an anionic open-framework with Al12P13O523- stoichiometry. As seen in Figure 6a, its structure is related to that of AlPO4-22 (aww topology) with 8-MR pore openings along c.17 In AlPO-CJB1, three kinds of cages exist, i.e., an aww cage, a P-incorporated aww cage, and an rpa cage (Figure 6b). The oxygen atoms of each PO4 group in the P-incorporated aww cage form four normal covalent bonds with adjacent Al atoms that become five-coordinated. In contrast to neutral framework AlPO4-n, the existence of AlO5 species confers the negative charge center onto the framework of AlPO-CJB1. Since no terminal P-O groups exist, the framework of AlPO-CJB1 is stable upon removal of the occluded protonated template molecules. Protons are left to balance the negative charged framework and act as Bro¨nsted acid centers. Similarly, in AlPO-CJB212,27 the strict alternation of Alcentered polyhdra (AlO4 and AlO6) and PO4 tetrahedra via all oxygen atoms forms an anionic 3-D open-framework with [Al11P12O48]3- stoichiometry (Figure 7). Its framework can be viewed as to be formed by stagger stacking of a series of 4.6.12-net layers along c. In summary, two situations will result in an anionic open-framework: (i) the existence of terminal P-O bonds and (ii) the occurrence of coordination numbers greater than four for Al atoms with the coordination sphere being bridging oxygens. Such situations have never been encountered in aluminosilicate zeolites. This explains why 484 ACCOUNTS OF CHEMICAL RESEARCH / VOL. 36, NO. 7, 2003

Apart from a class of 3-D open-framework structures, aluminophosphates also exhibit rich diversity in a variety of low-dimensional anionic frameworks, including 2-D layers, 1-D chains, and 0-D clusters constructed from alternation of various Al and P coordinations (Table 1). Stoichiometries of 2-D layered AlPO’s are found as AlPO4(OH)-,8,28 AlP2O83-,29-31 Al2P3O123-,32,33 Al3P4O163-,29,34-48 Al4P5O203-,49 and Al13P18O7215-,14 etc., among which the stoichiometry of Al3P4O163- is known in a number of 2-D layered compounds. With the exception of [Al3P4O16H]2[C3N2H5], which contains AlO5 units,29 the anionic sheets of Al3P4O163- are exclusively constructed from alternating AlO4 and PO3(dO) tetrahedra. Different linkages of these tetrahedra lead to various sheet topologies. Figure 8a shows eight distinct 2-D sheet structures, including 4.6.12-,35,39 4.6.8(I)-,34,38,41,47 4.6.8(II)-,44 4.6(I)-,36 4.6(II)-,37 4.6(III)-,42 4.6(IV)-,48 and 4.8-net.45 Five types of SBU’s for constructing the sheets are shown in the figure. Interestingly, the 2-D sheets exhibit various stacking sequences, such as AAAA,38,41 ABAB,34 ABCABC,46 and ABCDEF37 as seen in Figure 8b. The style of stacking is manipulated by the templating agent in the interlayer region which interacts with the inorganic frameworks through extensive H-bonds.43 A number of AlPO’s also occurs as 1-D anionic chains with stoichiometry of AlP2O83- 49-51 and Al3P5O20.6-52 The chains are made up of AlO4 tetrahedra and P(O-Al)nO4-n (n ) 1, 2, 3) tetrahedra with terminal P-OH and/or PdO groups. The corner-sharing 4-MR chains (AlPO-CSC) and edge-sharing 4-MR chains (AlPO-ESC) with Al/P ratio of 1/2 have the simplest chain structures. AlPO-CSC is made up of alternation of AlO4 and PO2bO2t tetrahedra to form linear corner-sharing Al2P2 4-MRs (Figure 9a). It has been proposed that such a 1-D chain, on hydrolysis and rotation of bonds, may transform to more complex framework structures.53 AlPO-ESC is made up of alternation of AlO4 units and PO4 units (PO3bOt and PObO3t) to form a zigzag ladder of fused Al2P2 4-MRs with pendant PO4H side groups (Figure 9b). Our studies show that the AlPO-CSC and AlPO-ESC chains can transform to each other under suitable synthetic conditions.

Assembly of 3-D Open-Frameworks Using 1-D Chain Building Units One important feature of low-dimensional AlPO’s is the existence of terminal PsOH and/or PdO groups. This implies that they might have potential to further condense to build up 3-D framework. The intact chains or fragments of AlPO-CSC and AlPO-ESC are featured in a variety of 2-D and 3-D AlPO structures. We believe that they are fundamental building units for the formation of AlPO’s. Of particular interest is the fact that these two types of


FIGURE 6. (a) Framework of AlPO-CJB1 viewed along c. (b) A side view showing the connection of three types of cages.

FIGURE 7. Framework of AlPO-CJB2 viewed along c (the 4.6.12-net sheet and SBU are shown). chain structures have also been found in zinc phosphates and other metal phosphates. Rao et al. have made use of the Aufbau Principle to provide a wonderful demonstration how the formation of complex zinc phosphates with open architectures involves a building-up process from such simple building units.8 Using AlPO-CSC as a building unit, 3-D open-frameworks MAlP2O8‚C2N2H9 have been successfully built up via transition metal cations (M ) Ni2+, Co2+, Fe2+).54,55 Figure 10 shows the framework structure of NiAlP2O8‚C2N2H9. The terminal oxygen atoms attached to the 1D AlP2O83- chains are exclusively coordinated to M2+, forming O-M-O bonds. The intact AlPOCSC chains along a and the -Ni-O-Ni- chains along c are cross-linked with each other to form open-framework containing 8-MR pore openings. Our studies also show that 3-D open-framework NiAlP2O8‚C2N2H9 can be built up from AlPO-ESC. This indicates that AlPO-ESC might be first transformed to AlPO-CSC followed by assembly to 3-D open-framework via Ni2+ cations. This work provides experimental evidence that 1-D AlPO-CSC and AlPO-ESC chains are important building units for the construction of complex open-frameworks.

Stoichiometries and Coordinations of Al and P Atoms in Aluminophosphates Aluminophosphates have been found with rich stoichiometries, which can be generally expressed as AlmPnO4n3(n-m)- (m ) 1, 2, 3 ..., n ) 1, 2, 3 ...). The Al coordinations occurring in these AlPOs are four, five, and six in the form of AlO3b(OH), AlO4b, AlO5b, AlO4b(OH), AlO4b(OH)2, AlO4b(H2O)2, AlO4b(OH)(H2O), AlO5b(OH), and AlO6b, while the P coordinations are solely four in the form of PO4b, PO3bOt, PO2bO2t, and PObO3t (b, bridging oxygens; t, terminal oxygens). Through alternation of different Al and P coordinations in the lattice, various stoichiometries can be generated. For example, the alternation of AlO4 and PO3bOt units restricts a stoichiometry of Al3P4O163-. We find that the Al/P ratio and the Al and P coordinations satisfy the following equation:

∑i mAlO

ib

× iAlOib )

∑j nPO

jb

× jPOjb

where i (j) is the number of bridging oxygens coordinated to Al (P), m (n) is the number of AlOib (POjb) coordination, ∑mAlOib/∑nPOjb ) Al/P, i ) 3, 4, 5, and 6, corresponding to VOL. 36, NO. 7, 2003 / ACCOUNTS OF CHEMICAL RESEARCH 485


FIGURE 8. (a) Eight distinct 2-D sheet structures and their SBU’s. (b) Packing of the sheets with four different stacking sequences. 486 ACCOUNTS OF CHEMICAL RESEARCH / VOL. 36, NO. 7, 2003


FIGURE 9. (a) Corner-sharing 4-MR chains (AlPO-CSC). (b) Edgesharing 4-MR chains (AlPO-ESC).

FIGURE 10. 3-D open-framework NiAlP2O8‚C2N2H9 (intact AlPO-CSC chains are retained in the structure). AlO3(OH), AlO4, AlO5, and AlO6 coordinations, respectively, and j ) 1, 2, 3, and 4, corresponding to PO4 tetrahedra with one, two, three, and four bridging oxygens, respectively. On the basis of this equation, the Al and P coordinations for a given stoichiometry can be enumerated. The importance of this equation is that coordinations for new stoichiometries, such as Al6P7O283-, Al7O8O323-, and so forth, could be easily enumerated. This will greatly help to design new structural topologies.

Design of Hypothetical Frameworks Aluminophosphates exhibit rich structure chemistry because of their diverse coordinations of Al and P atoms. Understanding of their structural construction regularities allows for the search of new topologies. Using computa-

tional method, aluminophosphates with specified stoichiometry can be designed. We have developed a method to systematically enumerate the 2-D nets with Al3P4O163stoichiometry.56, 57 The 2-D nets with Al3P4O163- stoichiometry are typically constructed from alternation of AlO4 and PO3(dO) tetrahedra via vertex oxygen atoms to form a 3.4-connection. The generation of such 2-D 3.4-connected meshes must satisfies the following conditions in topology: (i) there are two types of points, a three-connected point (P atom) and a four-connected point (Al atom); (ii) the same type of points cannot be directly connected according to the Lowenstein’s rule; (iii) the mesh must be expanded into a periodic 2-D net. Figure 11 shows the generation of a known 4.6.12-net starting from a hexagonal array of nodes (Figure 11a). Figure 11b illustrates the generation of a 2 × 2 mesh. By combining four child meshes (1) 3 × 2, (2) 2 × 2, (3) 3 × 2 and (4) 2 × 2 mesh, a final 5 × 4 mesh (5) is obtained (Figure 11c). This 5 × 4 mesh can be further expanded into the mesh of a 4.6.12-net in Figure 11d. Figure 11e shows the relaxed 4.6.12-net. After a series of computer procedures are performed, over 500 distinct 3.4-connected meshes with periodic arrangements have been generated. The generated 2-D nets include all known experimental sheets, as well as a variety of hypothetical sheets. Employing such a computational methodology, new topologies for aluminophosphates with various stoichiometries can be designed on the basis of the coordinations of Al and P atoms. Recently, Draznieks, and Fe´rey et al. developed a method for computational design of inorganic framework by automated assembly of SBUs.58 This will provide an excellent approach to design new open-frameworks based on various SBU’s of AlPOs. More recently, we have developed a computational methodology for the design of (4,2)-connected openframeworks with predefined pore geometry through constrained assembly of atoms in the unit cell.59 In this method, forbidden zones, corresponding to a porous pattern, are first defined in a unit cell, and then atoms are inserted based on specified symmetry and distance constraints (Figure 12a). For example, assuming a space group of P63/mmc, defining the pore radium of 6.0 Å and unique atoms of 2, a hypothetical open-framework consisting of extra-large micropore 18-MR channel is designed (Figure 12b). It contains columns of gme cages, each of which is connected through double 4-MRs. Employing this method, a number of known zeolite-like frameworks, as well as new hypothetical open-frameworks, can be generated. This method can be naturally applied to generate zeolite-like open-framework structures with extra-large micropore, crossed-linked channels, and chiral channels based on function requirements.

Computational and Combinatorial Approaches toward the Discovery of Aluminophosphates Aluminophosphates show fascinating structural architectures. What is of vital importance, however, is how to VOL. 36, NO. 7, 2003 / ACCOUNTS OF CHEMICAL RESEARCH 487


FIGURE 11. Generation procedure of a 4.6.12-net (a) axial system and unit cell of nodes in the generation of the mesh. (b) The generation of a 2 × 2 mesh. (c) The generation of a 5 × 4 mesh by combining four child meshes: (1) 3 × 2, (2) 2 × 2, (3) 3 × 2, and (4) 2 × 2. (d) The 4.6.12-net which is expanded from the 5 × 4 mesh. (e) the relaxed 4.6.12 net. approach to such diverse structures. The open-framework structures are greatly manipulated by organic amine templating agents located in the channels, in the interlayer or interchain regions which interact with the host framework through nonbonding interactions. Toward the discovery of aluminophoshates with specified structures, the selection of suitable templates is acknowledged to be of vital importance. We have recently developed a computational methodology to examine the templating ability of organic amines in the formation of 2-D layer and 3-D open-framework AlPO’s.43,60,61 In terms of the energies of the host-template nonbonding interactions, mainly Hbonding and van der Waals interactions, the templating ability of various organic amines for the inorganic hosts can be predicted. Some suitable template candidates can be selected that have lower interaction energies with a given host. One of the successful examples is the syntheses of Al4P5O19(OH)‚C5N2H16 (AlPO-PDA) and Al4P5O19(OH)‚ C4N3H15 (AlPO-DET) with structures analogous to that of AlPO-HDA by rational selection of 1,5-pentanediamine and diethylenetriamine as templates that are predicted by molecular simulations.60 488 ACCOUNTS OF CHEMICAL RESEARCH / VOL. 36, NO. 7, 2003

Since 1990s, our group has built up a synthesis database for microporous materials including aluminosilicate zeolites and open-framework metal phosphates. Recently, employing KDD (knowledge discovery of Database)62 strategy, we have successfully predicted the important synthetic factors determining the formation of aluminophosphates with 12-MR channels, with one of the successful examples being the rational synthesis of AlPO4-5.63 The KDD directed synthetic route will help to rationalize the synthesis of open-framework aluminophosphates with specified structures. On the other hand, the methodology of combinatorial chemistry will play a significant role in the discovery of new materials. Despite a large number of aluminophosphates have been found, the space of viable structure types is infinite. Recently, combinatorial approach has been successfully applied to the hydrothermal synthesis of open-framework materials.64 Using this approach an extensive study of complex multicomponent system is easily achieved, as shown in our recent work in the discovery of new zinc phosphates with novel framework architectures.65 Combinatorial chemistry will demonstrate its great strength in the discovery of open-framework


References

FIGURE 12. (a) The forbidden zones defined as cylinders in one unit cell. (b) The hypothetical framework containing18-MR channels with aperture dimensions of 9.4 Å x 9.4 Å (O‚‚‚O distance). The refined cell parameters are a ) 16.8 Å and c ) 14.3 Å. materials with new stoichiometries and interesting structural architectures and properties.

Conclusions The fascinating structure chemistry of a variety of aluminophosphates has been elucidated in this account. Aluminophosphates have been prepared with various structural dimensionalities, such as 3-D open-frameworks, 2-D layers, and 1-D chains, and with various stoichiometries. Compared to aluminosilicate zeolites built up from TO4 tetrahedra (T ) Si, Al), aluminophosphates possess diverse structural topologies because of their rich Al and P coordinations. The increasing interest in aluminophosphates derives from not only their growing chemical and structural diversity, but also from their promising applications as catalysts. Despite the large number of aluminophosphates that have been synthesized, the number of hypothetical topologies is infinite which can be designed by computational methods. The discovery of new materials will be dependent on the new preparative strategies. The use of computational methods such as molecular simulations and KDD technique will greatly assist in the rational synthesis of aluminophosphates with specified structures. On the other hand, combinatorial approach to hydrothermal synthesis will significantly accelerate the rapid discovery of new materials. This work was supported by the National Natural Science Foundation of China and the State Basic Research Project of China.

(1) Breck, D. W. Zeolite Molecular Sieves: Structure, Chemistry, and Use; Wiley: New York, 1973. (2) Wilson, S. T.; Lok, B. M.; Messian, C. A.; Cannan, T. R.; Flanigen, E. M. Aluminophosphate molecular sieves- a new class of microporous crystalline inorganic solids. J. Am. Chem. Soc. 1982, 104, 1146-1147. (3) Thomas, J. M.; Raja, R.; Sankar, G.; Bell, R. G. Molecular sieve catalysts for the regioselective and shape-selective oxyfunctionalization of alkanes in air. Acc. Chem. Res. 2001, 34, 191-200. (4) Raja, R.; Sankar, G.; Thomas, J. M. Bifunctional molecular sieve catalysts for the benign ammoximation of cyclohexane: one-step, solvent-free production ofoxime and epsilon-caprolactam with a mixture of air and ammonia. J. Am. Chem. Soc. 2001, 123, 81538154. (5) Thomas, J. M.; Raja, R.; Sankar, G.; Bell, R. G.; Lewis, D. W. Benign by design. new catalysts for an environmentally conscious age. Pure Appl. Chem. 2001, 73, 1087-1101. (6) Bennett, J. M.; Dytrych, W. J.; Pluth, J. J.; Richardson, J. W. Jr.; Smith, J. V. Structural features of aluminophosphate materials with Al/P ) 1. Zeolites 1986, 6, 349-361. (7) Cheetham, A. K.; Fe´ rey, G.; Loiseau, T. Open-framework inorganic materials. Angew. Chem., Int. Ed. Engl. 1999, 38, 3268-3292. (8) Rao, C. N. R.; Natarajan, S.; Choudhury, A.; Neeraj, S.; Ayi, A. A. Aufbau principle of complex open-framework structures of metal phosphates with different dimensionalities. Acc. Chem. Res. 2001, 34, 80-87. (9) Yu, J.; Li, J.; Xu, R. Structural diversity of a family of aluminophosphates with Al/P ratio of non-unity. Solid State Sci. 2000, 2, 181-192, and references therein. (10) Wang, K.; Yu, J.; Miao, P.; Song, Y.; Li, J.; Shi, Z.; Xu, R. A new layered aluminophosphate [C4H12N2][Al2P2O8(OH)2] templated by piperazine. J. Chem. Mater. 2001, 11, 1898-1902, and references therein. (11) Riou, D.; Loiseau, Th.; Fe´ rey, G. Structure determination of (N2C2H10)4(NH4)AlP4O16: A new sluminophosphate templated by ethylenediamine. J. Solid State Chem. 1992, 99, 414-418. (12) Yan, W.; Yu, J.; Shi, Z.; Miao, P.; Wang, K.; Wang, Y.; Xu, R. An anionic framework aluminophosphate |(CH2)6N4H3‚H2O|[Al11P12O48] and computer simulation of the template positions, Microporous Mesoporous Mater. 2001, 50, 151-158. (13) Yan, W.; Yu, J.; Xu, R.; Zhu, G.; Xiao, F.; Han, Y.; Sugiyama, K.; Terasaki, O. An anionic aluminophosphate molecular sieve with Bro¨ nsted acidity. Chem. Mater. 2000, 12, 2517-2519. (14) Tuel, A.; Gramlich, V.; Baerlocher, Ch. Synthesis, crystal structure and characterization of AP2DAO, a new layered aluminophosphate templated by 1,8-diaminooctane molecules. Microporous Mesoporous Mater. 2001, 47, 217-229. (15) Huo, Q.; Xu, R.; Li, S.; Ma, Z.; Thomas, J. M.; Jones, R. H.; Chippindale, A. M. Synthesis and characterization of a novel extra large ring of aluminophosphate JDF-20. J. Chem. Soc., Chem. Commun. 1992, 875-876. (16) Chen, J.; Pang, W.; Xu, R. Mixed-bonded open-framework aluminophosphates and related layered materials. Top. Catal. 1999, 9, 93-103. (17) Meier, W. H.; Olson, D. H.; Baerlocher, Ch. Atlas of Zeolite Structure Types; Elsevier: London, 2001. (18) Davis, M. E.; Saldarriaga, C.; Montes, C.; Garces, J.; Crowder, C. A Molecular sieve with eighteen-membered Rings. Nature 1988, 331, 698-699. (19) McCusker, L. B.; Baerlocher, Ch.; Jahn, E.; Bu¨ low, M. The triple helix inside the large-pore aluminophosphate molecular sieve VPI-5. Zeolites 1991, 11, 308-313. (20) Dessau, R. M.; Schlenker, J. L.; Higgins, J. B. Framework topology of AlPO4-8: the first 14-ring molecular sieve. Zeolites 1990, 10, 522-524. (21) Cerius2; Molecular Simulations/Biosym Corporation: San Diego, 1995. (22) Estermann, M.; McCusker, L. B.; Baerlocher, C.; Merrouche, A.; Kessler, H. Nature 1991, 352, 320-322. (23) Yu, J.; Sugiyama, K.; Zheng, S.; Qiu, S.; Chen, J.; Xu, R.; Sakamoto, Y.; Terasaki, O.; Hiraga, K.; Light, M.; Hursthouse, M. B.; Thomas, J. M. Al16P20O80H4‚4C6H18N2: A new microporous aluminophosphate containing intersecting 12- and 8-membered ring channels. Chem. Mater. 1998, 10, 1208-1211. (24) Wei, B.; G. Zhu, Yu, J.; Qiu, S.; Xiao, F.; Terasaki, O. Solvothermal synthesis and characterization of a new 3-D open-framework aluminophosphate [Al2P3O12][C4N3H16]. Chem. Mater. 1999, 11, 3417-3419. (25) Yan, W.; Yu, J.; Shi, Z.; Xu, R. A novel open-framework aluminophosphate [AlP2O6(OH)2][H3O] containing propeller-like chiral motifs. Chem. Commun. 2000, 1431-1432. VOL. 36, NO. 7, 2003 / ACCOUNTS OF CHEMICAL RESEARCH 489

Rich Structure Chemistry in Aluminophosphate Family Yu and Xu (26) Xu, Y.; Zhang, B.; Chen, X.; Liu, S.; Duan, C.; You, X. An open framework aluminophosphate with unique 12-membered ring channels: Al9(PO4)12(C24H91N16)‚17H2O. J. Solid State Chem. 1999, 145, 220-226. (27) Wang, K.; Yu, J.; Shi, Z.; Miao, P.; Yan, W.; Xu, R. Synthesis and characterization of a new three-dimensional aluminophosphate [Al11P12O48][C4H12N2][C4H11N2] with an Al/P ratio of 11/12. J. Chem. Soc., Dalton Trans. 2001, 1809-1812. (28) Yuan, H.; Chen, J.; Shi, Z.; Chen, W.; Wang, Y.; Zhang, P.; Yu, J.; Xu, R. Synthesis and structural characterization of a new layered aluminophosphate [C3H12N2][Al2P2O8(OH)2]‚H2O, J. C. S. Dalton Trans. 2000, 1981-1984. (29) Yu, J.; Williams, I. D. Two unusual layer aluminophosphates templated by imidazolium ions: [N2C3H5][AlP2O8H2‚2H2O] and 2[N2C3H5][Al3P4O16H]. J. Solid State Chem. 1998, 136, 141-144. (30) Morgan, K. R.; Gainsford, G. J.; Milestone, N. B. A new type of layered aluminium phosphate [NH4]3[Co(NH3)6]3[Al2(PO4)4]2 assembled about a cobalt(III) hexammine complex. Chem. Commun. 1997, 61-62. (31) Wei, B.; Yu, J.; Shi, Z.; Qiu, S.; Li, J. A new layered aluminophosphate [Al2P4O16][C6H22N4][C2H10N2] with 4.12-net porous sheets. J. Chem. Soc., Dalton Trans. 2000, 1979-1980. (32) Yu, J.; Sugiyama, K.; Togashi, N.; Hiraga, K.; Terasaki, O.; Qiu, S.; Xu, R. Synthesis and characterization of a new 2-D aluminophosphate layer [Al2P3O10(OH)2][C6NH8] and structural diversity in anionic aluminophosphates with Al2P3O123- stoichiometry. Chem. Mater. 1998, 10, 3636-3642, and references therein. (33) Chippindale, A. M.; Walton, R. I. [C9H20N][Al2(HPO4)2(PO4)]: An aluminium phosphate with a new layer topology. J. Solid State Chem. 1999, 145, 731-738, and references therein. (34) Jones, R. H.; Thomas, J. M.; Xu, R.; Huo, Q.; Cheetham, A. K.; Powell, A. V. J. Synthesis and structure of a novel aluminum phosphate anion - (Al3P4O16)3-. J. Chem. Soc., Chem. Commun. 1991, 1266-1268. (35) Thomas, J. M.; Jones, R. H.; Xu, R.; Chen, J.; Chippindale, A. M.; Natarajan, S.; Cheetham, A. K. A novel porous sheet aluminophosphate [Al3P4O16]3-1.5[NH3(CH2)4NH3]2+. J. Chem. Soc., Chem. Commun. 1992, 929-931. (36) Williams, I. D.; Gao, Q.; Chen, J.; Nagi, L.; Lin, Z.; Xu, R. Organictemplate control of inorganic structure: a low-symmetry twodimensional sheet aluminophosphate 3[NH3CHMeCH2NH3][Al6P8O32]‚H2O. Chem. Commun. 1996, 1781-1782. (37) Bruce, D. A.; Wilkinson, A. P.; White, M. G.; Bertrand, J. A. The synthesis and characterization of an aluminophosphate with chiral layers; trans-Co(dien)2‚Al3P4O16‚3H2O. J Solid State Chem. 1996, 125, 228-233. (38) Gao, Q.; Li, B.; Chen, J.; Li, S.; Xu, R.; Williams, I. D.; Zheng, J.; Barber, D. Nonaqueous synthesis and characterization of a new 2-Dimensional layered aluminophosphate [Al3P4O16]‚3[CH3CH2NH3]. J. Solid State Chem. 1997, 129, 37-44. (39) Chippindale, A. M.; Cowley, A. R.; Huo, Q.; Jones, R. H.; Law, A. D. Synthesis and structure of a new layered aluminium phosphate: [BuNH3]3[Al3P4O16]. J. Chem. Soc., Dalton. Trans. 1997, 2639-2643. (40) Gao, Q.; Chen, J.; Xu, R.; Yue, Y. Synthesis and characterization of a family of amine-intercalated lamellar aluminophosphates from alcoholic system. Chem. Mater. 1997, 9, 457-462. (41) Togashi, N.; Yu, J.; Zheng, S.; Sugiyama, K.; Hiraga, K.; Terasaki, O.; Yan, W.; Qiu, S.; Xu, R. Synthesis and structure of a 2-D layer Al3P4O16‚3CH3CH2CH2NH3. J. Mater. Chem. 1998, 8, 2827-2831. (42) Yu, J.; Li, J.; Sugiyama, K.; Togashi, N.; Terasaki, O.; Hiraga, K.; Zhou, B.; Qiu, S.; Xu, R. Formation of a new layered aluminophosphate [Al3P4O16][C5N2H9]2[NH4]. Chem. Mater. 1999, 11, 1727-1732. (43) Li, J.; Yu, J.; Yan, W.; Xu, Y.; Xu, W.; Qiu, S.; Xu, R. Structures and templating effect in the formation of 2D layered aluminophosphates with Al3P4O163- stoichiometry. Chem. Mater. 1999, 11, 2600-2606. (44) Yao, Y.; Natarajan, S.; Chen, J.; Pang, W. Synthesis and structural characterization of a new layered aluminophosphate intercalated with triply-protonated triethylenetetramine [C6H21N4][Al3P4O16]. J. Solid State Chem. 1999, 146, 458-463. (45) Vidal, L.; Gramlich, V.; Patarin, J.; Gabelica, Z. Synthesis, characterization and structure of Mu-7, a new layered aluminophosphate with a 4 × 8 Network. Chem. Lett. 1999, 201-202.

490 ACCOUNTS OF CHEMICAL RESEARCH / VOL. 36, NO. 7, 2003

(46) Yuan, H.; Zhu, G.; Chen, J.; Chen, W.; Yang, G. D.; Xu, R. Dual function of racemic 2-propanolamine as solvent and as template for the synthesis of a new layered aluminophosphate: [NH3CH2CH(OH)CH3]3Al3P4O16. J. Solid State Chem. 2000, 151, 145-149. (47) Tuel, A.; Gramlich, V.; Baerlocher, Ch. Synthesis, structure determination and characterization of a new layered aluminophosphate templated by piperazinium ions. Microporous Mesoporous Mater. 2001, 46, 57-66. (48) Vidal, L.; Gramlich, V.; Patarin, J.; Gabelica, Z. Synthesis and structure of Mu-4, the new layered aluminophosphate [(C2H5)2NH2]4[Al8P10O40H2][H2O]2.5. Eur. J. Solid. State Chem. 1998, 35, 545-563. (49) Jones, R. H.; Thomas, J. M.; Xu, R.; Huo, Q.; Xu, Y. Cheetham, A. K.; Bieber, D. J.; Synthesis and structure of a one-dimensionally extended aluminum phosphate Et3NH+(H2AlP2O8)-. J. Chem. Soc., Chem. Commun. 1990, 1170-1172. (50) Gao, Q.; Chen, J.; Li, S.; Xu, R. Synthesis and structure of a chain aluminophosphate filled with [NH4]+ and [H3NCH2CH2NH3]2+ cations. J. Solid State Chem. 1996, 127, 145-150. (51) Williams, I. D.; Yu, J.; Gao, Q.; Chen, J.; Xu. R. New chain architecture for a one-dimensional aluminophosphate, [H3NCH2CH2NH3][AlP2O8H]. Chem. Commun. 1997, 1273-1274. (52) Oliver, S.; Kuperman, A.; Lough, A.; Ozin, G. A. Aluminophosphate chain-to-layer transformation. Chem. Mater. 1996, 8, 2391-2398. (53) Oliver, S.; Kuperman, A.; Ozin, G. A. A New model for aluminophosphate formation: transformation of a linear chain aluminophosphate to chain, layer and framework structures. Angew. Chem., Int. Ed. Engl. 1998, 37, 46-62. (54) Wei, B.; Yu, J.; Shi, Z.; Qiu, S.; Yan, W.; Terasaki, O. A 3-D openframework nickel aluminophosphate [NiAlP2O8][C2N2H9]: Assembly of 1-D AlP2O83- chains through [NiO5N] octahedra. Chem. Mater. 2000, 12, 2065-2067. (55) Wang, K.; Yu, J.; Song, Y.; Xu, R. Assembly of one-dimensional AlP2O83- chains to three-dimensional framework MAlP2O8‚C2N2H9 through transition metal cations (M ) Ni2+, Co2+ and Fe2+)”. J Chem. Soc., Dalton Trans. 2003, 99-103. (56) Zhou, B.; Yu, J.; Li, J.; Xu, Y.; Xu, W.; Qiu, S.; Xu, R. Rational design of 2-D layered aluminophosphates with Al3P4O163- stoichiometry. Chem. Mater. 1999, 11, 1094-1099. (57) Zhou, B.; Li, J.; Yu, J.; Xu, Y.; Xu, W.; Qiu, S.; Xu, R. Systematic enumeration of two-dimensional layered aluminophosphates with [Al3P4O16]3- stoichiometry. Comput. Chem. 1999, 23, 555-563. (58) Draznieks, C. M.; Newsam, J. M.; Gorman, A. A.; Freeman, C. M.; Fe´ rey, G. De novo prediction of inorganic structures developed through automated assembly of secondary building units (AASBU). Angew. Chem., Int. Ed. Engl. 2000, 39, 2270-2275. (59) Li, Y.; Yu, J.; Liu, D.; Yan, W.; Xu, R.; Xu, Y. Design of zeolite frameworks with defined pore geometry through constrained assembly of atoms. Submitted. (60) Yu, J.; Li, J.; Wang, K.; Xu, R.; Sugiyama, K.; Terasaki, O. Rational synthesis of microporous aluminophosphates with inorganic open-framework analogous to Al4P5O20H‚C6H18N2. Chem. Mater. 2000, 12, 3783-3787. (61) Yu, J.; Li, J.; Xu, R. Towards rational design and synthesis of aluminophosphates with 2-D layer and 3-D open-framework structures. Microporous Mesoporous Mater. 2001, 48, 47-56. (62) Fayyad, U. M., Piatetsky-shapiro, G., Smyth, P.; Uthurusamy, R., Eds. In Advances in Knowledge Discovery and Data Mining; AAAI Press: Menlo Park, CA, 1996. (63) Liu, X.; Xu, Y.; Yu, J.; Li, Y.; Zeng, W.; Chen, C.; Li, J.; Pang, W.; Xu, Y.; Xu, Y. Rational synthesis of microporous aluminophosphates with the aid of Data Mining. Chem. J. Chin. Univ. (in Chinese), in press. (64) Akporiaye, D. E.; Dahl, I. M.; Karlsson, A.; Wendelbo, R. Combinatorial approach to the hydrothermal synthesis of zeolites. Angew. Chem., Int. Ed. Engl. 1998, 37, 609-611, and references therein. (65) Song, Y.; Yu, J.; Li, G.; Li, Y.; Wang, Y.; Xu, R. Combinatorial approach for the hydrothermal synthesis of open-framework zinc phosphates. Chem. Commun. 2002, 1720-1721.

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